EP0008849B2 - Process for preparing acrylonitrile polymer fiber - Google Patents
Process for preparing acrylonitrile polymer fiber Download PDFInfo
- Publication number
- EP0008849B2 EP0008849B2 EP79301263A EP79301263A EP0008849B2 EP 0008849 B2 EP0008849 B2 EP 0008849B2 EP 79301263 A EP79301263 A EP 79301263A EP 79301263 A EP79301263 A EP 79301263A EP 0008849 B2 EP0008849 B2 EP 0008849B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- water
- polymer
- molecular weight
- acrylonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000835 fiber Substances 0.000 title claims description 67
- 229920002239 polyacrylonitrile Polymers 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920000642 polymer Polymers 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000007711 solidification Methods 0.000 claims description 23
- 230000008023 solidification Effects 0.000 claims description 23
- 230000004927 fusion Effects 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- 229920002972 Acrylic fiber Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000002074 melt spinning Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 238000000578 dry spinning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- GRPFBMKYXAYEJM-UHFFFAOYSA-M [4-[(2-chlorophenyl)-[4-(dimethylamino)phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-dimethylazanium;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C(=CC=CC=1)Cl)=C1C=CC(=[N+](C)C)C=C1 GRPFBMKYXAYEJM-UHFFFAOYSA-M 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- -1 carpet Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
Definitions
- This application relates to a process for preparing acrylonitrile polymer fibre.
- a preferred procedure for conducting this process is to spin the fusion melt directly into a steam-pressurized solidification zone which controls the rate of release of water from the nascent extru-- date to prevent deformation thereof as it leaves the spinnerette and enables a high degree of filament to be obtained.
- Stretching of the extruded fiber is preferably carried out in the solidification zone.
- the process of the present invention is characterized by the use of an acrylonitrile polymer which is a copolymer, containing at least 1 mol percent of comonomer, and which has a number average molecular weight of at least 6,000 but less than 15,000, and by conducting stretching of the extrudate in the steam-pressurized solidification zone in two stages so as to provide a total stretch ratio of at least 25, with the first stage of stretching being at a stretch ratio less than that of the second stage.
- an acrylonitrile polymer which is a copolymer, containing at least 1 mol percent of comonomer, and which has a number average molecular weight of at least 6,000 but less than 15,000
- a preferred processing step is that of drying the stretched extrudate under coditions of temperature and humidity to remove water therefrom while avoiding formation of a separate water phase therein. After such drying, it is generally preferred to conduct steam-relaxation on the dried extrudate under conditions which provide shrinkage thereof to the extent of 15-40%.
- the process of the present invention unexpectedly provides acrylonitrile polymer fiber of useful physical properties for many applications in spite of the fact that it employs polymers of number average molecular weight values that are reported to be too low to provide fiber of any value.
- the fiber obtained by the process of the present invention has desirable physical properties that render it useful in many industrial applications as well as for textile purposes depending upon processing stems conducted thereon.
- the fiber obtained by the process of the present invention has physical properties that are equivalent to many of the current acrylonitrile polymer fibers commercially offered and, therefore are useful in those same applications that the commercial acrylonitrile polymer fibers are employed.
- the fiber obtained by the process of the present invention is useful in textile, carpet, paper and other industrial applications.
- the composition of the fiber-forming acrylonitrile polymer used in the present invention will be the same as any of those previously known fiber-forming acrylonitrile polymers but the acrylonitrile polymer used in the present invention will differ therefrom in number average molecular weight.
- the acrylonitrile polymer used in the present invention will have a number average molecular weight of at least 6,000 but less than 15,000, preferably 7,500 to 14,500.
- polymerization should be conducted so as to provide the proper number average molecular weight in accordance with conventional procedures.
- the number average molecular weight values (M n ) reported in the present application were determined by gel permeation chromatography using a Waters Gel Permeation Chromatograph, cross-linked polystyrene gel column packing and dimethyl formamide-0.1 molar lithium bromide solvent.
- the chromatograph was calibrated using a set of four acrylonitrile polymers for which Nf, and the weight average molecular weight (M n ) has been determiend by membrane osmometry and light scattering measurements, respectively.
- the GPC calibration constants were determined by adjusting them to get the best fit between M n and M w values and values calculated from the chromatograms of polydisperse samples.
- Useful polymers for the process in accordance with the present invention are copolymers of acrylonitrile and one or more monomers copolymerizable therewith. Such polymers will contain at least 1 mol percent of comonomer, preferably at least 3 mol percent thereof. The copolymer will contain at least about 50 mol percent of acrylonitrile preferably at least 70 mol percent thereof.
- a suitable acrylonitrile polymer Once a suitable acrylonitrile polymer has been selected, it is necessary to provide a homogeneous fusion melt of the polymer and water at a temperature above the boiling point of water at atmospheric pressure and at a superatmospheric pressure sufficient to maintain water and polymer as a homogeneous fusion melt.
- the particular temperatures and pressures useful will vary widely depending upon polymer composition but can readily be determined following prior art teachings, which also teach the proper proportions of polymer and water necessary to provide a homogeneous fusion melt.
- the homogeneous fusion melt After the homogeneous fusion melt is provided, it is spun through a spinnerette directly into a steam-pressurized solidification zone.
- the steam-pressurized solidification zone is maintained under conditions such that the rate of release of water from the nascent extrudate is controlled so as to prevent deformation of the extrudate as it emerges from the spinnerette.
- the extrudate After the extrudate exits from the solidification zone, it may be further processed in accordance with conventional procedures.
- Such drying provides fiber of improved transparency and improved dye intensity.
- the acrylonitrile polymer fiber provided by the present invention is typical of acrylonitrile polymer fibers in general and differs therefrom essentially only in the number average molecular weight of the fiber-forming polymer, the present invention employing a lower number average molecular weight value.
- homopolymers of acrylonitrile are contemplated in the prior art as fiber-forming polymers, the present invention requires at least 1 mol percent of comonomer in the polymer composition to provide processability.
- the present invention in spite of its use of low molecular weight fiber-forming polymers, provides acrylonitrile polymer fiber that has physical property values well within the range of typical acrylic fiber properties and in many cases exceeds these values.
- An acrylonitrile polymer containing 89.3% acrylonitrile and 10.7% methyl methacrylate was prepared according to conventional suspensions procedures to provide a polymer having a - number average molecular weight of 20,500.
- the isolated polymer cake was dried to obtain a powder containing 18.1% water.
- the polymer-water mixture was heated under autogeneous pressure in a screw extruder to provide a fusion melt at 180°C.
- the resulting melt was spun through a spinnerette directly into a steam-pressurized solidification zone maintained at 22 pounds per square inch gauge pressure (1.52 bar).
- the nascent extrudate was subjected to two stages of stretching while in the solidification zone, a first stage at a stretch ratio of 2.3 and a second stage at a stretch ratio of 10 to provide a total stretch ratio of 23.
- the resulting 3.7 denier per filament tow was relaxed in steam at 124°C to provide fiber of 5.3 denier per filament (d/f). Properties of the relaxed fiber are given in Table I which follows.
- Comparative Example B The procedure of Comparative Example B was repeated in every material detail except that the polymer had a number average molecular weight of 13,200, the fusion melt was processed at 195°C, the solidification zone was maintained at 18 psig (1.24 bar), the first stage stretch was at a stretch ratio of 3.3 and the second stage stretch was at a stretch ratio of 13.8 to provide a total stretch ratio of 44, and the 2.3 d/f fiber was relaxed in steam at 124°C to provide a 3.25 d/f fiber. Properties of the fiber are also given in Table I.
- Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 89.7% acrylonitrile and 10.3% methyl methacrylate and had a number average molecular weight of 12,300; the polymer contained 18.3% water and was processed at 190°C; the solidification zone was maintained at 18 psig (1.24 bar), the first stage stretch was at a stretch ratio of 2.6 and the second stretch stage was a stretch ratio of 17 to provide a total stretch ratio of 46; and the resulting 3.9 d/f fiber was relaxed in steam at 124°C to provide a 5.1 d/f fiber. Physical properties are also given in Table I.
- Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 88.4% acrylonitrile and 11.6% methyl methacrylate and had a number average molecular weight of 11,200; the polymer contained 18.6% water and was processed at 169°C; the solidification zone was maintained at 12 psig (0.83 bar), the first stage stretch was at a stretch ratio of 6.1 and the second stretch stage was at a stretch ratio of 7.2 to provide a total stretch ratio of 43.9; and the resulting 2.9 d/f fiber was relaxed in steam at 120°Cto provide a 4.1 d/ffiber. Physical properties are also given in Table I.
- Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 88.6% acrylonitrile and 11.4% methyl methacrylate and had a number average molecular weight of 7,900; the polymer contained 13.1% water and was processed at 180°C; the solidification zone was maintained at 11 psig (0.76 bar), the first stretch stage was at a stretch ratio of 4.5 and the second stretch stage was at a stretch ratio of 7.1 to provide a total stretch ratio of 31.9; and the 3.0 d/f fiber was relaxed in steam at 120°C to provide a 4.3 d/ffiber. Physical properties are also given in Table I.
- Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 88.4% acrylonitrile and 11.6% methyl methacrylate and had a number average molecular weight of 11,200; the polymer contained 13.5% water and was processed at 170°C; the solidification zone was maintained at 12 psig (0.83 bar), the first stretch stage was at a stretch ratio of 3.8 and the second stretch stage was at a stretch ratio of 12.2 to provide a total stretch ratio of 46.4; and the 3.2 d/f fiber was relaxed in steam at 125°C to provide a 5.0 d/ffiber. Physical properties are also given in Table I.
- Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 87.6% acrylonitrile, 11.9% methyl methacrylate and 0.5% 2-acrylamido-2-methylpropanesulfonic acid and had a number average molecular weight of 14,400; the polymer contained 15.5% water and was processed at 171°C; the solidification zone was maintained at 11 psig (0.76 bar), the first stretch stage was at a stretch ratio of 3.7 and the second stretch stage was at a stretch ratio of 10.7 to provide a total stretch ratio of 39.4; and the 2.2 d/f fiber was relaxed in steam at 125°C to provide at 3.4 d/f fiber. Physical properties are also given in Table I.
- the fiber provided by Comparative Example B has considerably greater straight and loop tenacity values than the commercial acrylic fibers prepared by wet-spinning and dry-spinning procedures.
- the fiber prepared by Examples 1 and 2 also have greater straight and loop properties than the commercial acrylic fibers.
- the fibers prepared by Examples 3-6 all have properties within the ranges of values provided by commercial acrylic fibers in spite of the low molecular weight of the fiber-forming acrylonitrile polymers.
- Comparative Example B The procedure of Comparative Example B was again followed in every material detail except for the acrylonitrile polymer employed.
- a polymer containing 88.9% acrylonitrile and 11.1 % methyl methacrylate and having a number average molecular weight of 4,500 it was not possible to successfully spin a fusion melt of the polymer and water because an unsatisfactory fiber resulted. This indicates that an acrylonitrile polymer of this number average molecular weight value is unsuitable as a fiber-forming polymer.
- the polymer contained 88.5% acrylonitrile and 11.5% methyl methacrylat.e and had a number average molecular weight of 5,300. Spinnability of a fusion melt with water of this polymer was marginal and proper processing to provide fiber for determination of physical properties could not be accomplished.
- the minimum number average molecular weight of an acrylonitrile polymer for spinning as a fusion with water was about 6,000, preferably about 7,500.
- Example 6 The procedure of Example 6 was again followed in every material detail except that the stretched fiber was dried for 23 minutes in an oven maintained at a dry bulb temperature of 138°C and a wet bulb temperature of 74°C. The dried fiber was then relaxed in steam to provide a shrinkage of 30%. The fiber obtained was tested in accordance with the following procedures.
- a sample of fiber is dyed with Basic Blue 1 at 0.5 weight percent, based on the weight of fiber, to complete exhaustion.
- the dyed sample is then dried in air at room temperature and a reflectance measurement is made versus a control using the Color-Eye at 620 millimicrons.
- the control sample is a commercial wet spun acrylic fiber of the same denier dyed and handled in the same manner as the experimental fiber. The result is reported as the percent reflectance of that achieved by the control. In the case where the experimental fiber has more void structure than the control, there will be more light scattered and the dyed experimental fiber will register less than 100% reflectance at 620 millimicrons. The fiber will also appear to the eye to be lighter in color than the control.
- a twenty gram sample of carded and scoured fiber is dyed with 0.5 weight percent of Basic Blue 1 based on the weight of fiber, at the boil until complete exhaustion occurs.
- One portion of the dyed fiber is dried in air at room temperature.
- Another portion is dried in an oven at 300°F (149°C), for 20 minutes. Reflectances of both samples are obtained using the Color-Eye at 620 millimicrons. The change in reflectance of the over-dried sample relative to the reflectance of the air dried sample is the shade change.
- the dye intensity of the fiber obtained in Example 7 was 72 and the shade change was 13.
- the fiber obtained in Example 6 which was not dried under conditions of controlled temperature and humidity prior to relaxation, was subjected to the same dye tests, the fiber exhibited a dye intensity of 40 and a shade change of 13.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT79301263T ATE928T1 (de) | 1978-08-30 | 1979-06-29 | Polyacrylnitrilfasern und verfahren zu deren herstellung. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US938201 | 1978-08-30 | ||
| US05/938,201 US4219523A (en) | 1978-08-30 | 1978-08-30 | Melt-spinning acrylonitrile polymer fiber from low molecular weight polymers |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0008849A1 EP0008849A1 (en) | 1980-03-19 |
| EP0008849B1 EP0008849B1 (en) | 1982-04-28 |
| EP0008849B2 true EP0008849B2 (en) | 1986-01-08 |
Family
ID=25471087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79301263A Expired EP0008849B2 (en) | 1978-08-30 | 1979-06-29 | Process for preparing acrylonitrile polymer fiber |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US4219523A (fi) |
| EP (1) | EP0008849B2 (fi) |
| JP (1) | JPS5536391A (fi) |
| AR (1) | AR217932A1 (fi) |
| AT (1) | ATE928T1 (fi) |
| BR (1) | BR7904642A (fi) |
| CA (1) | CA1127815A (fi) |
| CS (1) | CS252805B2 (fi) |
| DD (1) | DD145642A5 (fi) |
| DE (1) | DE2931439A1 (fi) |
| ES (1) | ES483588A1 (fi) |
| GR (1) | GR72262B (fi) |
| HU (1) | HU178416B (fi) |
| IE (1) | IE48680B1 (fi) |
| IN (1) | IN152486B (fi) |
| MX (1) | MX150675A (fi) |
| PH (1) | PH15994A (fi) |
| PL (1) | PL117369B1 (fi) |
| PT (1) | PT69924A (fi) |
| RO (1) | RO85024B1 (fi) |
| TR (1) | TR21462A (fi) |
| YU (1) | YU40375B (fi) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4524105A (en) * | 1977-11-17 | 1985-06-18 | American Cyanamid Company | Melt-spun acrylonitrile polymer fiber of improved properties |
| US4301107A (en) * | 1978-08-30 | 1981-11-17 | American Cyanamid Company | Melt-spinning a plurality of acrylonitrile polymer fibers |
| DE2951803A1 (de) * | 1979-12-21 | 1981-07-02 | Bayer Ag, 5090 Leverkusen | Feinsttitrige synthesefasern und -faeden und trockenspinnverfahren zu ihrer herstellung |
| US4278634A (en) * | 1980-08-18 | 1981-07-14 | American Cyanamid Company | Biconstituent acrylic fibers by melt spinning |
| FR2489455B1 (fr) * | 1980-09-04 | 1986-04-11 | Valeo | Garniture de friction, notamment pour freins, embrayages et autres applications |
| US4421707A (en) * | 1982-04-29 | 1983-12-20 | American Cyanamid Company | Acrylic wet spinning process |
| US4515859A (en) * | 1982-09-16 | 1985-05-07 | American Cyanamid Company | Hydrophilic, water-absorbing acrylonitrile polymer fiber |
| US4935180A (en) * | 1988-08-25 | 1990-06-19 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers |
| US4981751A (en) * | 1988-08-25 | 1991-01-01 | Basf Aktiengesellschaft | Melt-spun acrylic fibers which are particularly suited for thermal conversion to high strength carbon fibers |
| US5168004A (en) * | 1988-08-25 | 1992-12-01 | Basf Aktiengesellschaft | Melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers |
| US4921656A (en) * | 1988-08-25 | 1990-05-01 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers which are particularly suited for thermal conversion to high strength carbon fibers |
| US4981752A (en) * | 1989-07-06 | 1991-01-01 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers which are well suited for thermal conversion to high strength carbon fibers |
| US4933128A (en) * | 1989-07-06 | 1990-06-12 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers which are well suited for thermal conversion to high strength carbon fibers |
| KR950005429B1 (ko) * | 1991-03-27 | 1995-05-24 | 한국과학기술연구원 | 무방사 내열성 아크릴 단섬유 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2585444A (en) * | 1948-07-29 | 1952-02-12 | Du Pont | Preparation of shaped articles from acrylonitrile polymers |
| US3984601A (en) * | 1971-10-14 | 1976-10-05 | E. I. Du Pont De Nemours And Company | Acrylonitrile polymer filaments |
| US3896204A (en) * | 1972-10-02 | 1975-07-22 | Du Pont | Melt-extrusion of acrylonitrile polymers into filaments |
| US4094948A (en) * | 1972-10-02 | 1978-06-13 | E. I. Du Pont De Nemours And Company | Improved acrylonitrile polymer spinning process |
| IL43990A (en) * | 1973-02-05 | 1976-08-31 | American Cyanamid Co | Method of spining fiber using a fusion-melt polymer composition |
| SE403141B (sv) * | 1973-02-05 | 1978-07-31 | American Cyanamid Co | Smeltspinningsforfarande for framstellning av en akrylnitrilpolymerfiber |
| US3873508A (en) * | 1973-12-27 | 1975-03-25 | Du Pont | Preparation of acrylonitrile polymer |
| US3991153A (en) * | 1975-06-24 | 1976-11-09 | American Cyanamid Company | Single phase extrusion of acrylic polymer and water |
| GB1527004A (en) * | 1976-11-01 | 1978-10-04 | Japan Exlan Co Ltd | Process for the melt-shaping of acrylonitrile polymers |
| US4205039A (en) * | 1977-11-17 | 1980-05-27 | American Cyanamid Company | Process for melt-spinning acrylonitrile polymer fiber |
-
1978
- 1978-08-30 US US05/938,201 patent/US4219523A/en not_active Expired - Lifetime
-
1979
- 1979-06-18 CA CA329,987A patent/CA1127815A/en not_active Expired
- 1979-06-19 IN IN631/CAL/79A patent/IN152486B/en unknown
- 1979-06-29 EP EP79301263A patent/EP0008849B2/en not_active Expired
- 1979-06-29 AT AT79301263T patent/ATE928T1/de not_active IP Right Cessation
- 1979-07-06 GR GR59531A patent/GR72262B/el unknown
- 1979-07-11 AR AR277254A patent/AR217932A1/es active
- 1979-07-16 PT PT69924A patent/PT69924A/pt unknown
- 1979-07-20 BR BR7904642A patent/BR7904642A/pt not_active IP Right Cessation
- 1979-08-02 DE DE19792931439 patent/DE2931439A1/de active Granted
- 1979-08-03 MX MX178767A patent/MX150675A/es unknown
- 1979-08-16 PH PH22916A patent/PH15994A/en unknown
- 1979-08-21 RO RO98502A patent/RO85024B1/ro unknown
- 1979-08-21 TR TR21462A patent/TR21462A/xx unknown
- 1979-08-23 ES ES483588A patent/ES483588A1/es not_active Expired
- 1979-08-28 DD DD79215236A patent/DD145642A5/de unknown
- 1979-08-28 HU HU79AE579A patent/HU178416B/hu not_active IP Right Cessation
- 1979-08-29 CS CS795888A patent/CS252805B2/cs unknown
- 1979-08-29 PL PL1979218011A patent/PL117369B1/pl unknown
- 1979-08-29 IE IE1650/79A patent/IE48680B1/en not_active IP Right Cessation
- 1979-08-30 YU YU2118/79A patent/YU40375B/xx unknown
- 1979-08-30 JP JP10980979A patent/JPS5536391A/ja active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| BR7904642A (pt) | 1980-04-15 |
| DE2931439A1 (de) | 1980-03-20 |
| EP0008849B1 (en) | 1982-04-28 |
| ES483588A1 (es) | 1980-04-16 |
| DD145642A5 (de) | 1980-12-24 |
| PT69924A (en) | 1979-08-01 |
| DE2931439C2 (fi) | 1992-01-23 |
| JPS6233327B2 (fi) | 1987-07-20 |
| PH15994A (en) | 1983-05-20 |
| PL218011A1 (fi) | 1980-06-16 |
| CS252805B2 (en) | 1987-10-15 |
| IE48680B1 (en) | 1985-04-17 |
| EP0008849A1 (en) | 1980-03-19 |
| YU40375B (en) | 1985-12-31 |
| IN152486B (fi) | 1984-01-28 |
| PL117369B1 (en) | 1981-07-31 |
| MX150675A (es) | 1984-06-27 |
| JPS5536391A (en) | 1980-03-13 |
| YU211879A (en) | 1983-01-21 |
| US4219523A (en) | 1980-08-26 |
| IE791650L (en) | 1980-02-29 |
| RO85024A2 (ro) | 1984-08-17 |
| CA1127815A (en) | 1982-07-20 |
| GR72262B (fi) | 1983-10-10 |
| CS588879A2 (en) | 1987-03-12 |
| RO85024B1 (ro) | 1984-09-30 |
| TR21462A (tr) | 1984-06-18 |
| HU178416B (en) | 1982-05-28 |
| ATE928T1 (de) | 1982-05-15 |
| AR217932A1 (es) | 1980-04-30 |
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